US9394219B2 - Method for producing synthesis gas for methanol production - Google Patents

Method for producing synthesis gas for methanol production Download PDF

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US9394219B2
US9394219B2 US14/354,531 US201214354531A US9394219B2 US 9394219 B2 US9394219 B2 US 9394219B2 US 201214354531 A US201214354531 A US 201214354531A US 9394219 B2 US9394219 B2 US 9394219B2
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gas mixture
gas
methanol
synthesis gas
synthesis
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US20140256994A1 (en
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Gaetano Iaquaniello
Barbara Cucchiella
Elena Antonetti
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Stamicarbon BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series

Definitions

  • the present invention relates to synthesis gas production from light hydrocarbons such as natural gas.
  • the present invention relates to the production of synthesis gas particularly suitable for methanol production.
  • methanol plants produce methanol in several steps, usually including synthesis gas preparation (reforming), methanol synthesis and methanol purification. Since these steps are conducted in separate process sections, the technology for each section can be selected and optimised independently. The usual criteria for the selection of technology are capital cost and plant efficiency. The preparation of synthesis gas and compression typically accounts for about 60% of the total investment, and almost all energy is consumed in this process section. Therefore, the technology to produce synthesis gas is of major importance.
  • the invention presents, in one aspect, a method for producing synthesis gas from a hydrocarbon containing feed, comprising the steps of:
  • FIG. 1 schematically shows a conventional method wherein use is made of a combined reformer with a pre-reforming section.
  • the present invention provides a method for producing synthesis gas, which synthesis gas is particularly suitable for use in methanol production.
  • a synthesis gas suitable for methanol production means that the synthesis gas has a certain ratio of components, especially of hydrogen and carbon oxides, which is optimal for methanol synthesis.
  • methanol synthesis gas can be characterised by a molar ratio (H 2 ⁇ CO 2 )/(CO+CO 2 ), referred to herein as an R ratio.
  • An R ratio equal to 2 corresponds to a stoichiometric synthesis gas for formation of methanol.
  • the synthesis gas obtained according to the method of the present invention has preferably an R ratio in the range of 1.90-2.20, more preferably 1.95-2.05.
  • a hydrocarbon containing feed is provided.
  • Any hydrocarbon containing feed suitable for steam reforming can be used.
  • the feed contains light hydrocarbons such as C 1-4 alkanes, e.g. methane, ethane, etc. More preferably, the feed contains methane or a gas containing substantial amounts of methane, preferably natural gas. It is preferred to use a desulfurised feed. Therefore, if needed, the hydrocarbon containing feed can be subjected to a desulfurisation step.
  • the hydrocarbon containing feed is subjected to catalytic partial oxidation (CPO).
  • CPO catalytic partial oxidation
  • This typically involves a reaction of hydrocarbons with steam and oxygen in the presence of a catalyst.
  • the reaction can be represented as follows: CH 4 +0.60 O 2 ⁇ 1.95 H 2 +0.85 CO+0.15 CO 2 +0.05 H 2 O
  • the R ratio of the product is typically 1.87.
  • the reaction is typically performed in the presence of a metal catalyst.
  • the catalytic metal is preferably a Group VIII noble metal, e.g., platinum, iridium, rhodium, osmium, ruthenium, although nickel may also be used as the catalytic metal.
  • the oxygen used in the catalytic partial oxidation process may be pure or substantially pure oxygen or an oxygen containing gas, e.g., air, or a mixture of oxygen with an inert gas. Substantially pure oxygen (that is, containing more than 99% oxygen) is particularly preferred, and pure oxygen containing more than 99.9% oxygen is still more preferred.
  • the hydrocarbon containing feed Prior to the CPO reaction, the hydrocarbon containing feed, or at least part of it, is preferably subjected to pre-reforming.
  • part of a feed it is understood to encompass more than 0% but less than 100% of the feed, hence not including the end points “0%” and “100%”.
  • the part can be 0.1-99.9%, or 1-99% of the feed, or any other value not being 0% and 100%.
  • higher hydrocarbons higher than C 1
  • methane oxygen consumption in the CPO reactor is thereby minimised.
  • Adiabatic steam reforming can be used for pre-reforming.
  • the steam-to-carbon molar ratio is preferably from 1.5 to 2, more preferably from 1.6 to 1.7.
  • the feed can be preheated to the pre-reforming temperature which is, preferably, in the range of 250-600° C., more preferably 450-550° C. and in particular about 475° C.
  • the pre-reforming temperature which is, preferably, in the range of 250-600° C., more preferably 450-550° C. and in particular about 475° C.
  • the preheating can conveniently be done by exchanging heat with a stream leaving a process gas boiler.
  • a high-temperature stream leaving the CPO reactor is cooled down and can be used to preheat the pre-reforming feed in a gas-gas exchanger.
  • the feed supplied to the CPO reactor is preferably preheated to a temperature of 200-500° C., preferably 350-450° C. and in particular to a temperature of about 400° C. At these temperatures, the supply of oxygen to the CPO reactor is minimised. This also reduces the costs for the air separation unit (ASU), in case the latter is used to supply oxygen for the CPO reaction.
  • the hydrocarbon containing feed and the oxygen can be in various ratios in the feed gas mixture. The precise mixture introduced into the reaction zone depends on the particular hydrocarbons used and the amount of oxygen necessary to conduct the partial oxidation reaction. Operable ratios can be easily determined by one skilled in the art. Usually, the O 2 /C (Oxygen to Carbon) ratio is in the range 0.4-0.6, preferably about 0.5.
  • CPO (also often referred to as SCT-CPO) is known to the skilled person.
  • SCT-CPO refers to Short Contact Time Catalytic Partial Oxidation.
  • the CPO reaction takes place in a reactor under the influence of a catalyst at residence times between 10 ⁇ 2 to 10 ⁇ 4 and with typical catalyst surface contact times around 10 ⁇ 6 s ⁇ 1 . These contact time correspond to typical space velocities of 100,000 to 250,000 hr ⁇ 1 , preferably 100,000 to 200,000 hr ⁇ 1 .
  • Catalysts employed for SCT-CPO comprise Ni, Pd, Pt, Rh, or Ru.
  • the reaction takes place at catalyst surface temperatures above 950° C., preferably above 1000° C.
  • a reference to CPO is (a) L. Basini, Catalysis Today 117 (2006) 384-393. Other references include (b) L. Basini, K. Aasberg-Petersen, A. Guarinoni, M. Oestberg, Catalysis Today (2001) 64, 9-20 “Catalytic Partial Oxidation of Natural Gas at Elevated Pressure and Low Residence Time”; (c) H. Hickman, L. D. Schmidt, J. Catal. 138 (1992) 267; (d) D. Hichman, L. D.
  • a first gas mixture comprising hydrogen (H 2 ), carbon monoxide (CO) and carbon dioxide (CO 2 ) is formed.
  • the mixture is preferably cooled in a process gas boiler and then divided into two streams.
  • the first gas mixture after the CPO process contains less carbon dioxide than in a conventional CRT process. This is particularly advantageous in methanol plants, which require a CO 2 content as low as possible.
  • the first gas mixture comprises less than 10 vol. % CO 2 on dry basis, more preferably less than 6 vol. % CO 2 on dry basis.
  • the CO/CO 2 ratio of the first gas mixture is preferably from 5 to 15, and more preferably about 10.
  • Part of the first gas mixture is then subjected to a water gas shift (WGS) reaction to adjust the CO/CO 2 ratio of the gas mixture, the untreated part being a first remaining gas mixture.
  • WGS water gas shift
  • carbon monoxide together with extra steam is converted to additional hydrogen and carbon dioxide, yielding a second gas mixture.
  • the CO/CO 2 ratio is preferably reduced to a value 3 to 10, more preferably to a value from 6 to 7. By modifying the amount of gas by-passing the WGS reactor, the CO/CO 2 ratio can conveniently be adjusted.
  • At least part of the second gas mixture originating from the WGS reaction is further subjected to hydrogen purification, preferably by pressure swing adsorption (PSA), to separate CO 2 and obtain a hydrogen containing gas mixture.
  • part of the second mixture is subject to hydrogen purification, that is up to but not including 100 vol. %.
  • the untreated part of the second gas mixture if present) is referred to herein as a second remaining gas mixture.
  • pure hydrogen with a purity higher than 99% is obtained.
  • the purge gas obtained during hydrogen purification e.g. in a PSA unit, can suitably be supplied to the CPO reactor or added to the hydrocarbon containing feed before the desulfurisation step.
  • the unshifted part of the first gas mixture (first remaining gas mixture) is combined with the part of the second gas mixture not subjected to hydrogen purification (second remaining gas mixture), if present, and with at least part of the hydrogen obtained during hydrogen purification, to obtain a synthesis gas particularly suitable for methanol synthesis.
  • first remaining gas mixture the part of the second gas mixture not subjected to hydrogen purification
  • second remaining gas mixture the part of the hydrogen obtained during hydrogen purification
  • the composition of the gas obtained in the CPO reaction is first adjusted with respect to the CO/CO 2 ratio through the WGS reaction and then with respect to the H 2 /CO ratio by the addition of pure hydrogen.
  • the R ratio of the synthesis gas is raised in this way to above 1.9, and preferably to about 2.
  • the part of the reformed feed (first gas mixture) that is branched off for the WGS reaction may be chosen based on the feed composition and on the subsequent application of the synthesis gas, particularly methanol synthesis. It is preferred to use up to 50 vol. % of the feed in the WGS reaction, such as from 5 to 50 vol. %, more preferably from 10 to 40 vol. %. In an alternative embodiment, 5 to 20 vol. % of the first gas mixture is subjected to the WGS reaction. Preferably 20-100 vol. % of the shifted feed (second gas mixture), more preferably from 20 up to but not including 100 vol. %, is further subjected to hydrogen purification, preferably, by PSA. In a preferred embodiment, 40-80 vol. % is subjected to hydrogen purification, such as 50-70 vol. %.
  • the final synthesis gas is used for methanol production, it is particularly advantageous to subject 5 to 15 vol. % of the first gas mixture to the WGS reaction and 40 to 60 vol. % of the second gas mixture to hydrogen purification.
  • a particularly preferred embodiment includes about 10 vol. % and about 50 vol. % of the respective feeds.
  • the proportions of different feeds can be varied in broad ranges, such as, for example, from 5 to 50 vol. % of the first gas mixture subjected to the WGS reaction, in combination with 50-100 vol. % of the second gas mixture subjected to hydrogen purification.
  • the present invention relates to a method for producing methanol from a hydrocarbon containing feed.
  • the method comprises the steps previously described to obtain a synthesis gas, which synthesis gas is then used to produce methanol. Any suitable method to produce methanol from synthesis gas can be used.
  • carbon oxides and hydrogen from the synthesis gas react on a catalyst to produce methanol.
  • the catalyst for this reaction usually contains copper and zinc.
  • Using a CPO reaction to produce synthesis gas makes it possible to keep the CO 2 content lower than in the conventional technology. This is particularly advantageous for the plants where the CO 2 amount is required to be limited. Moreover, a high CO/CO 2 ratio during the methanol synthesis increases the reaction rate and conversion and also decreases the water formation, which in turn reduces the catalyst deactivation rate.
  • Another advantage is associated with the startup of the process, when the optimum temperature of the reaction is not yet reached and the product composition deviates from the desired composition. Since the composition of the end product can easily be varied by varying the ratio of different gas streams, the process of the invention allows a quicker startup of the production of any downstream processes e.g. methanol production.
  • a further advantage is that by applying the method of the invention, the economy of synthesis gas production is improved.
  • the method results in a reduction of costs, e.g., because it allows to produce syngas with a desired composition without the need to install expensive process units such as a steam reformer (SR) and an autothermal reformer (ATR), as conventionally used in the prior art.
  • SR steam reformer
  • ATR autothermal reformer
  • the invention allows to produce synthesis gas for methanol production with a negligible or even zero CO 2 emission into the atmosphere.
  • FIG. 1 illustrates a known combined technology process.
  • a natural gas feed 100 is desulfurised in a hydrodesulfurisation (HDS) reactor 1 .
  • a desulfurised feed 120 is then subjected to preheating in a convection section 50 of a steam reformer (SR) 5 .
  • Preheated stream 121 is mixed with steam and supplied to a pre-reformer 11 , whereafter the stream is split into two feed streams, 122 and 123 .
  • Stream 122 is supplied to the steam reformer 5 , in which natural gas together with steam is catalytically converted to a synthesis gas 124 .
  • Stream 123 is mixed with synthesis gas 124 and both are fed into an autothermal reformer (ATR) 2 .
  • ATR autothermal reformer
  • the mixed gas stream together with oxygen is reformed to a synthesis gas 106 , which has a proper composition to be used (after compression) for methanol synthesis in a synthesis reactor 6 .
  • FIG. 2 shows an embodiment according to the present invention, wherein synthesis gas for methanol production is obtained.
  • a natural gas feed 100 is desulfurised in a HDS reactor 1 .
  • the feed stream 101 is then preheated using heat exchange with a gas stream of a process gas boiler 3 and introduced, after adding steam, to a pre-reforming section 11 .
  • stream 108 is then combined with stream 109 to form stream 110 , which is a synthesis gas having an H 2 /CO ratio equal to 3 and an R ratio (H 2 ⁇ CO 2 )(CO+CO 2 ) equal to 2, thereby having a particularly suitable composition to enter a methanol production unit 6 .
  • the splitting ratio for streams 104 / 105 depends on the feed composition, presence of a pre-reforming section and on the specific syngas application. For methanol application using natural gas as feed and a pre-reforming at 475° C. such ratio is preferably 80/20 (vol).
  • the subsequent ratio 106/107 is preferably 50/50 (vol).
  • pre-reforming may be omitted.

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